Patent GB-650940-A (GB)
Title: Improvements in or relating to the production of water-soluble derivatives of dialkylolamides of dimerized polyunsaturated fatty acids
IPC: D06P1/649
Filed: 1947-06-03
Abstract: Water-soluble condensates are prepared by condensing dialkylolamides of dimerized polyolefinic fatty acids of the general formula <FORM:0650940/IV (a)/1> wherein R is the residue of a dimerized polyolefinic fatty acid whose monomer contains 18-20 carbon atoms, n is a whole number from 2 to 4, R1 is hydrogen or the radical -CnH2n OH, with a sufficient quantity of an alkylene oxide having 2 to 4 carbon atoms to render the product soluble, said quantity of alkylene oxide being at least 8 mols. per mol. of the dimer acid diamide. Condensation may be effected in the presence of polar solvents such as isopropanol or t-butanol.  Starting materials include the di-alkylolamides derived from mono- and di-ethanolamines, ethanol-propanolamine, ethanol-butanolamine, propanolamine and butanolamine and dimerized cottonseed fatty acids, linseed fatty acids, soya bean fatty acids, tung oil fatty acids, hydrated castor oil fatty acids and fish oil fatty acids. The examples illustrate the process using ethylene oxide and products containing up to 175 ethenoxy units are prepared; reference is made to the use of propylene and butylene oxides. The products may be used as dispersing and emulsifying agents and in dyeing textile materials with a preformed metallized dye soluble in an acid bath, examples being given (see Group IV (c)). Specification 650,939, [Group IV (b)], is referred to.ALSO:Water-soluble derivatives of dialkylolamides of dimerized polyolefinic fatty acids of the general formula <FORM:0650940/IV (b)/1> wherein R is the residue of a dimerized polyolefinic fatty acid, the monomer of which contains 18-20 carbon atoms, n is a whole number from 2 to 4, R1 is hydrogen or the radical -CnH2nOH, are prepared by condensing the dialkylolamide with a sufficient quantity of an alkylene oxide having 2 to 4 carbon atoms to render the product water-soluble, said quantity of alkylene oxide being at least 8 mols. per mol. of the dimer acid diamide.  The condensation may be effected in the absence of solvents by heating the dimer acid diamide with ethylene, propylene or butylene oxide in an autoclave under pressure, preferably in the presence of an alkaline condensation catalyst such as sodium alcoholate at 100-160 DEG  C.; alternatively, condensation may be effected at lower temperatures and generally at atmospheric pressure by use of polar solvents such as isopropanol or t-butanol, preferably with the addition, as catalyst, of a lower alkylamine such as di- or tri-ethylamine, and then the alkylene oxide may be passed into the solution of amide under reflux conditions.  The amount of alkylene oxide required for optimum results may vary widely; with the lower molecular weight diamides, such as the bis-ethanolethanolamides, as little as 8 mols. of ethylene oxide, 10-15 mols. of propylene oxide and 15-25 mols. of butylene oxide for each mol. of dimer acid diamide will produce adequate water-solubility.  The products are stated to have good dispersing and emulsifying properties and to be valuable as assistants in dyeing processes employing preformed metallized dyes in an acid dye bath (see Group IV (c)).  The alkylol amides employed as starting materials may be prepared by the method described in Specification 650,939, and from the various reactants therein specified.  According to typical examples: (1) N,N1-di-2-hydroxyethylamide of dimerized cottonseed fatty acid (190 gms.) in t-butanol is heated under reflux in presence of triethylamine and ethylene oxide (244 gms.) bubbled through the solution over 12 hours, after which solvent and unreacted material is distilled off, leaving a dark viscous liquid product; (2) as in (1) using 21 gms. ethanol amide and 266 gms. ethylene oxide, the product obtained containing 175 ethenoxy units per molecule, the bis-diethanolamide of dimerized cottonseed fatty acid is similarly reacted with 16 mols. of ethylene oxide; (3) bis-monoethanolamide of dimerized linseed fatty acid (0.151 mol.) is similarly reacted with ethylene oxide until 2.84 mols. have been absorped, the product being a dark red oil; (4) bis-monoethanolamide of dimerized tung fatty acid (0.156 mol.) is reacted as in (1) with in one case 2.93 mols. ethylene oxide and in another case with 4.95 mols. ethylene oxide both products being dark oils; (5) the reaction of (1) is repeated using 0.149 mol. of bis-monopropanolamide of dimerized cottonseed fatty acid and 3.86 mols. of ethylene oxide.  In these examples, the alkylolamides are prepared by refluxing a xylene solution containing 1 mol. of the dimerized acid or its dimethyl ester and 2 mols. of monoethanolamine while distilling off the water produced and sometimes an additional 10 per cent molecular excess of the amine is added near the end of the reaction since some of the amine may tend to distil off with the water.ALSO:Textile materials are dyed with a preformed metallized dye soluble in an acid bath containing the dye and a water-soluble derivative of a dialkylol amide prepared by condensing a dialkylolamide having the general formula <FORM:0650940/IV (c)/1> wherein R is the residue of a dimerized polyolefinic fatty acid the monomer of which contains 18-20 carbon atoms, n is a whole number from 2 to 4 inclusive, and R1 is hydrogen or -CnH2nOH, with a sufficient quantity of an alkylene oxide having 2-4 carbon atoms to render the product soluble, said quantity being at least 8 mols. per mol. of dimer acid diamide (see Group IV (b)). According to examples (9)-(11), wool yarn is dyed in an aqueous acid dye bath containing as dyeing assistant the product obtained by reacting N,N1 - di - 2 - hydroxyethylamide of dimerized cotton seed fatty acid (190 gms.) and ethylene oxide (244 gms.) and as dye stuff (a) the chromium complex of the azo dyestuff from diazotized anthranilic acid and 1-(41-sulphophenyl)-3-methyl-5-pyrazolone, (b) said chromium complex, diazotized 1 - amino - 2 - hydroxynaphthalene - 4 - sulphonic acid coupled to 1 - phenyl - 3 - methyl - 5 - pyrazolone and diazotized 1 - amino - 2 - hydroxy - naphthalene - 4 - sulphonic acid coupled to 1-hydroxy - naphthalene - 8 - sulphonic acid, and (c) the chromium complex of the azo dyestuff obtained from diazotized 1-amino-2-hydroxy - 6 - nitro - naphthalene - 4 - sulphonic acid coupled to 2-naphthol, respectively, and to example 12; wool yarn is dyed in an acid bath containing the chromium complex of the azo dyestuff obtained from diazotized 4-nitro-2-amino-phenol coupled to 1-(41-sulphophenyl)-3 - methyl - 5 - pyrazolone and as assistant the product obtained by reacting the bis-monoethanolamide of dimerized linseed oil fatty acid (0.151 mol.) and ethylene oxide (2.84 mols.).  The resulting dyeing shows improved brightness, levelness and strength of shade as compared with the same dyeing carried out in the absence of the alkylolamide products.  Other alkylolamide products mentioned are the ethylene oxide, propylene oxide and butylene oxide condensation products derived from bis - ethanolamides, propanolamides, butanolamides, ethanol-propanol amides and ethanol-butanol amides of dimerized fatty acids from cottonseed oil, soya bean oil, dehydrated castor oil, linseed oil, tung oil and fish oils.  The products also have dispersing and emulsifying properties.